Methylol derivatives of ureido-polyamines



for a Patented Nov. 4, 1952 UNITED PATENT omcs ME THYLOD DERIVATIVES OF UREIDO a PQLYAMINES y Roberts, Yost, Oreland, and Robert Auten, I

Jenkintown, Pa gassignors to Rol m k; Haas Delaware Company, Phila'delphia, Pa a corporation of Nopr wina Anp fi nIJ i 1 195 Serial No. 237,664

12Claims.-

' This inventionu relates U to novel nitrogenous esine fiomr s t qes qh a e art larly use: l. f r treatin aper t mp tt ereto imn ve ife eit s e eeqial y elei qntoi e ls rsn hl ese co pos ion o r pered-j.

h i niionalso on ern a r cess. wh r b The present application is a continuation-inea s m t 201W, ridv pw ban e'ned' e e .0 i his. nven a QIQPX WS a e ssl j i tep b e by efi ed; y l esr polyarnines, dihaloalkanes, a urea, and formal; ehy ela mb nedie a 'suqses qnp steps m iie j a e elu e. or fiqn -lr r 1di =t the fs' f ese ste a ql e h enen ly min v n a l lar ht. e t. l 161 and preferably at least 189: is reacted in solut ion with f l a q liana We t hre arb n oms 1. lli 5 1 9 e t es Pro u 15 P iscohdensed- Withurea by heating it therewith; h e iil l pendant i th n emai luti' vvi thformaldehyde withigrprescribedproa to 'give a resinous composition which is 'a-rly useful for improving the wet ii en thp g ape end ns ies rea a ermahebyd re. of

course, well known. n have e r r e t es of t n u mpo i ion hi enti n, m ler ias aiie e e.

v i'f e tin l Q Yimi EQ QPKl q emine i h .es'e ss of; a eelpelk e an fz s een urt er Pr po ed o. r. harden. s sh resi with n hy e or" an;mayamb m ldenis w sthei Sachiflwhbls r fs es har t memo t he, water-S ble,1 1191 5. ,a qmri posit ons provided by the present; inyention,

F r th in ial tee e sam n o th s. er a e a t du flih lealka a d? a ent; Y v Delv l leneiz ram na h .rdihalqa k acq tains; two N to three carbon atoms with chlori flb fbmineroasl he .p rrede qe n here m y: thu use :lfl-Phlerwthe 1 27 2 191 m ma:

moethane, 1, 2-dich10ropropane, 1,2; pane, ,or mixed halogen compounds the di'ha loalkane in each instance having a chain ofitwo ee pms tw at he e e is-o a The polyamine should have a minimum molecular size corresponding to a weight of at least 146, although it is preferred that the polyamine have a minimum molecularweight oi189. I There isno sharp upper limit to the sizelot thepoly- Yt .for practical purposes-- an upper limit for the molecular size of the starting marte'rialfi'of' about 559- on average includes most of th'e variousspecies that are available.- The-polyamines.

hey l e e e e tl.

2 amines are prepared usuallyv as mixtures, although triethylenetetramine and tetraethylenepenta-mineare available in products each boilin'gyover a range of about 30 C. and contain- 1 mg to of asingle compound; Higher polyethlenepolyamines are obtained as a residue which it is diificu-lt to fractionate. There is evidence that these preparations contain materials:

havingtertiary amine groups as well as primary and secondary groups,

For the preparation of above polyethylenepolyamines one may takea more readily available amine, such as diethylenetriamine or ethyl-i enediamine, and react such amine with one, of the dihaloalkanes defined above or a mixture thereof to form a polyalkylenepolyamine hydr0- halide, which is then reacted with a base such as sodium hydroxide or sodium carbonate to give free polyamine of the molecular size defined above. The product of this preliminary reaction is fully equivalent to the commercial ma: terials' already described.-

This preliminary condensation is' desirably performed with 0.25 to 0.75 moles of a dihaloal- 'kane per mole -ofethylenediamine, 1,2-propylenediamine, trimethylenediamine, diethylenetriamine, -or mixtures thereof. The direct condensate is an-aminehydrohalide, the hydrohali'de (of which-is destroyed byrea-ction with'an alkaline reagent. The resulting polya-lkylenepolyamine is 'thenready for reaction with a-dihaloalkane,- just as the triethylenetetramine or other'higher polyethylenepolyamine shown above.

A dihaloalkane and polyethylenepolyamine both meeting --the above limitations, are reacted,

preferably in solution in an inert solvent, he tweenflO? and C., and if necessary, under pressure. Water or a short chained saturated monohydric alcohol or mixture of these liquids 60%-- of the reactionmixture is solvent.

. 3 of dihaloalxane and polyamine fall within the ratios of 0.7 :1 and 15:1 and are such that they yield a soluble condensate when reacted in solution. The above ratios are by moles.

The condensation of polyalkylene polyamine and dihaloalkane may be carried out in one step or in a series of steps. If a series of steps is used, the hydrchalide may be neutralized at each step, if so desired. In a stepwise procedure the total amount of dihaloalkane may in some cases be somewhat above the 1.621 ratio and yet soluble condensates are still produced.

Under these conditions, the products which result reach a molecular range at which the visco-sities of their aqueous solutions containing 60% to 65% solids come within the range at 25 C. of N to Z: on the Gardner-Holdt scale and preferably U to Z1. The reaction is then interrupted. Sufiicient alkali may be added here to convert the polyamine hydrohalide to the free polyamine. A small excess of alkali does not interfere with subsequent reactions. The resulting salt may be left in the reaction mixture, although itcan be removed, if desired. 'In the preferred process solvent is stripped off at this point to yield the material to be subjected to the'stepnext to be describedreaction with urea. It is not, however, essential to strip ofi solvent at this point, except to ensure that a temperature at least sufficient to start evolution of ammonia can be reached. This temperature is usually near 110 C. If the temperature is carried above this'point, solvent is taken off rapidly and the rate of reaction will increase.

If the hydrohalide is not destroyed by addition of alkali, as shown above, the amine hydrohalide may nevertheless be used in the subsequent step of reacting with urea. Under these conditions the final product may not be quite so effective for improving the wet strength of paper as the product which results after the hydrohalide is destroyed. Yet the final product made with a polyamine hydrohalide as an intermediate is a very useful one.

. In the next step the product from reaction of dihaloalkane and polyethylenepolyamine is reacted with urea. The amount of the urea needed depends upon the -NI-I groups available forreaction in the above product. The ratio of urea to ,NH groups may vary from 0.2:1 to 1.511. The preferred ratios are from 0.5:1 to 12:1. The product and urea are mixed and heated. Reaction between them begins in therange of about 100 to 110 C. with evolution of ammonia. The

rate of reaction increases as the temperature increases until at about 160 C. evolution of ammonia is complete in 15 to minutes. Temperatures may be-carried to 200 C., a range of 100 to 200 C. being suitable- When water is not present the preferred temperature range is 120 to 150 C. and the reaction is continued until a 50% aqueous solution of the solids has a viscosity of about B to M at C. on the Gardner-Holdt scale. It is preferred that the reaction be interrupted when the viscosity of the solution is C to H. If the reaction. between the reaction product of dihaloalkane'with polyethylene-polyamine and urea isperformed in an aqueous system, the temperature of the reacting mixture under reflux at atmospheric pressure is about 112 .C. In this case the reaction is continued until the same viscosities are reached. In any case, the reaction is stopped before gelation has started so that the reaction product with .urea remains fully soluble. The product is cooled and reduced pressure or it may be dried, as by spray 4 dissolved in water to give a 20% to 70% solution for use in the next operation.

In this operation the reaction product formed with urea is reacted in aqueous solution with formaldehyde. The reaction is carried out at 20 to 100 C About 0.6 to 1.5 moles of formaldehyde, I-ICHO, is used per hydrogen on nitrogen atom in the above reaction product, including the hydrogen on free urea present therein. The upper limit is not sharp. No deleterious effects result from use of excess formaldehyde. On the other hand enough formaldehyde must be taken to yield a stable product. With ratios less than 0.5 to 1 the resulting resinous product has been observed to gel in a day or two.

The hydrogen atoms available for reaction can be calculated by considering the original nitrogen content of the dihaloalkane-polyamine reaction product and the extent of reaction of of polyamine and urea can be gauged by the amount of ammonia evolved in the reaction with urea.

A sample calculation will illustrate the application of these considerations. A dihaloalkanepolyethylenepolyamine condensate and urea are mixed in the proportions of 12 equivalents of the former (based on NH groups) and 12 moles of urea, this being a 1:1 ratio of urea to --NH. This mixture is heated with evolution of five moles of ammonia. There are, therefore, reacted five moles of urea, providing ten hydrogen equivalents. S'even equivalents of -NH groups remain unreacted, the difference between equivalents taken and ammonia evolved. By the same token seven moles of urea remain in the fusion mixture, each mole supplying four equivalents of hydrogen. There are then 45 equivalents of hydrogen, for which formaldehyde should be supplied. If the formaldehyde condensate ratio is to be 0.9 to 1, 40.5 equivalents of formaldehyde will be mixed with this polyamine-urea condensate.

. The formaldehyde is usually used in a 30% to 37% aqueous solution, but even more concentrated solutions may be used such as those supplying 40 to 50% available formaldehyde. It may, if desired, be also supplied at least in part from a revertible polymer. The solution of product from the reaction of polyamine and urea is mixed with formaldehyde. The resulting reaction mixture maybe heatedv at im-100 C. to complete the reaction. A resinous condensate. in solution results. 'It maybe used directly in this form or it may be concentrated; as by'evaporation under drying. It may be mixed with a soluble ureaformaldehyde condensate or melamine-formaldehyde condensate.

Typical preparations of the soluble resinous products of this invention are given in detail in the following examples. Parts are by weight.

Example 1 Therewas dissolved 94.5 parts by weight of a tetraethylenepentamine of 88% purity in parts of water. Theretowasadded 49.5 parts of ethylene dichloride. The mixture was stirred and heated under' reflux for four hours. The pot temperature at this time was 111 C. This reast ma set le, mix-tyre had a. tisc s y or on lo .scaleat 6Q%;,so1 ds.- Itwa di l r w th ,6 a ts. and tr ed w th s s d i m. hydro ide.-

l. mchle i e wasp ace inthe amou a l9lt Thiswes qu yalen to he use f'fioapar 0f the e.'Wates was"d sti ed,- f ,.unde owv th ves elws eated on an. -1 bathneqybyr itrat pn- "Th emp ature at W ammonia ,evqltution e an was 7 11439 he aised to' 0;. and

emheratu ewas a a held at this level for anho There wasadded AG- 4$ tint? nwestaken, Thi by al lat n; QIl nfi r. -TQJQQQWQE QT ".hydmgem; o 5 mole) of a 36% assets armaments .t h mixtur lw hute lr dine 7-5 was heated to 95 '0. for? a ts; o a s u ion. Qf' r e u I n e s ona is Zara areal-s lids or -3 f r s sol heser this solution was 7.4.;

' 1 olut n} was e ed-hi hly e e ti e o iaigrqr z heetstrenethef nan I ram; 2 There was charged: to a reaction vessel 1069 parts hyrweight-ot ethylene: d chl rid and; M0

parts :of-water. The mixture was stirred and t ere o was added; -1 Phil parts; oft t a thy1 ne pentamine. The, heat. of solution? caused the temp ratureof the. mixture. to rise C h mix re; as he t d un l fl x e W r upon the heat of reaction maintained the tern nerature" f; the r acti n. mixtu at fluxin temperatures for: aboutian; hour. The" reaction mixture; was-then heatedandstirred until; the

. viscosity; f the mixture was); on the Gardner'- Hol vs ae;

"A port moi 318,:parts ofthe reaction mixture was: treated; ith;.fI28 par s: of a- 50.-9%1. sodium i. ,and, 216 parts of-urea:wastherr added; This; mixture was: stirred and heated with: water-being distilledoff 7 under, re-

ducedypressure; The; temperature was: carried to? l I 010. undenlow pressure-r Normal pressure wasgesto fed and: the; batch -heat ed 1 at 130"135 Ge -Qr 15- 1mm;- T e; viscosi of a5 aqu u solutio ofthe resulting product was D on the Ga elf Hd1Ql I Sa1Q;-At this point 195 parts ofgwater was addedwand the mixture stirred until? homogeneouav Thea-resulting mixture was 7 cooled to; 3091C; whereupon-' 1220;parts of an aqueous 37.6%,formaldehyde solution was addedand tirred into; the amine-urea condensate.

Th viscosity ofr-theresulting solution-was B1 c theeardner-Holdt s This condensate was "applied to paper pulp at the wet end of the paper making machine. It was found to impart excellent wet strength to; papers. from 01316301186. or unbleached sulfite on;.-.kraft pulpsm It'is effective in amounts of 0;251%:"to5% on the weight-of the dry fiber, Itistgives': high early wet: strengths and wet strengthsiincrea'se fon some days after'the paper has Kbeen: made. It-gives higher strengths at lowzconcentrations, such as /4% to 1%, than the-,resiris which have-hereto ore been proposed 'li es 1l i...e so u on containi h a ov a e a iqnpro uq l T e ac n e e wa 179 the resid ei l a ded ar s o w s e olv d; a orbed in Wate and forExthi's purpose. It gives higher -strengthsat 75.

There were mixed 147 parts byweight of; pro; e e h o e; 8 a s ,te aet ir e ep m tamine; and 1 160' parts, of" water. mix re was stirred and heated at j 12Q-f1'30 jCffoif hi hQurs i in "a a nles te tlqs a e-f c, a this time the pressure increased from 30p; s. to 160 p. s. 1., apparently'due to formation of a volatile by-product. The solution of the'resulte" ing' product was cooled, and treated withi22ll parts of a caustic soda solution.

There were mixed 155 parts of the above solu; tion and 72 parts of I urea: This mixture was heated with stirring under reduced pressureito a temperature of 110 C. afterwhich theT'esjidue; was heated at l=l8vto 155"? C: until 9 .-7parts ':of a eme h' d'b e e Th meot eati i as oneho e d en. m nu es. he e, werethen: added IOOparts-of "Water and3 iparts or 36%,, formaldehyde solution; This mixturewas stirred 'with gentle heating for a halfhour; The visq t o of he s l ina olut on was A; jibh 1' er Ho dts a a. tr enta n d e2. lid d t D fl tQtIlBYSOI t OI TW p odu s e e i ei q f; mp ns' e et;

! Emmpled The procedure of Example. 3 was followedexcept thatpafter addition of. the"50% sodiumhy-z. droxide' solution to react with amine hydrochloride the solution washeated under lowpress lre. Water was thereby distilled Ofi to yieldfa: mix; ture of salt and polyamino product; Thislmixture was refluxed with isopropyl alcohol, whereby the polyamino producti'was; dissolved, The.

alcoholic solution wasfiltered-i to separate the; salt. Theufiltrate wasgsubjectedgto distillation;- to remove-the alcohol.

Therewas, then mixed 50? partsyor the result: ing residue and ,72; parts of urea in 200,parts. of water; This; reaction mixture was heated to 13.0? C. for-a half hour." The'resulting product-j when m'ade into a 50% aqueous solutionimparted thereto a-viscosityt'of on'the Gardner-Holdt.

; scale. This solution Was'reacted with 645 parts of a 36% formaldehyde solution andthe result-x ingvmixture warmed until the resulting solution had aviscosity of Ann the Gardner- Holdt scale; he product. a en ia l h same properti s; as thosedescribed-abovq Eicdmple In this example there is illustratedthe;build: ing up-of an amine of considerablesizein a, series of steps, In the first step diethyIenetriamine which itself does not directly give a-polyethy1- enepolyamine of the size requiredto yield a'final product offull effectiveness inwetstrengthapplications, is used to yield; astarting polyamine of the size and type which will yield the pre ferred high molecular polyamines.

To 18.7 parts of diethylenetriamine which had been heated to 0. there was slowly added Withj,gOOd; agitation 12.6 parts i of ethylene di-' chloride." Durlngrthis addition the temperature;

of the reaction mixture was kept at 105-110 C., cooling being required at first and toward the end of the addition heating being necessary to maintain the desired temperature. When the addition of the above ethylene dichloride was complete, the reaction mixture was heated to 120 .C. and held at this temperature until the viscosityof a sample thereof diluted with water in a ratio of 2:1 was between D and E at 25 C. on the Gardner-Holdt scale. The mixture was cooled and treated with 20.4 parts of aqueous 50 sodium hydroxide solution.

The reaction mixture was then heated to 105 C." and 10.8 parts of ethylene dichloridewas slowly added with good agitation and with maintenance of temperature between 105-110 C. The mixture was heated at 112 C. until the reaction mixture from which salt was allowed to settle'had a viscosity of W to W+ on the Gardner-Holdt scale. The mixture was cooled to 100 C. and treated with 17.5 parts of aqueous 50% sodium hydroxide solution.

The reaction mixture was again heated to 105-110 C. and 8.6 parts of ethylene dichloride were gradually added over a 2.5 hour period. The mixture was heated at 112 C. under reflux of water until the viscosity of the reaction mixture from which salt was centrifuged was about X on the Gardner-Holdt scale. The mixture was cooled .and treated with 13.9 parts of aqueous 50% sodium hydroxide solution.

' In the first step above the molar ratio of diethylenetriamineto ethylene dichloride was 120.69. In the second and third steps combined the ratio was 1*:1-148. If this ratio is increased to 1:16,

there results a gel which is still water-soluble, but which is not readily handled in the subsequent operations. Use of still more ethylene dichloride in the above steps leads to a gel which gives entirely unsatisfactory final products.

The polyamine of large molecular size as prepared above was heated under reduced pressure until about half of the water content of the polyamine preparation had been distilled off. The'concentrate was then treated with 37.5 parts of urea and heated under reduced pressure until the temperature thereoi reached 100 C. at 20 mm. pressure. Heating was continued under normal pressure. Evolution of ammonia beganat about 105 C. The temperature of the mixture was raised to 135 C. and held at this level until a sample of the reaction mixture diluted with an equal weight of water gave a viscosity of C on the Gardner-Holdt scale.

This reaction product was diluted with 18.2 parts of water with the temperature kept at about 100 C. and then was cooled to about 50 C. It was treated with 222 parts of aqueous 37% formaldehyde solution. There was thus prepared a resin solution containin 42.1% of total solids. The resin solids mounted to 30%. The Viscosity of the solution was B on the Gardner-Holdt scale.

This product gives a'very good wet strength Example 6 In this example there is shown the conversion of ethylenediamine to a polyethylenepolya The above mine which is then carried to a largenioleculai size by further stepwise reaction with ethylene dichloride. The final product resulting after reaction with urea and then reaction with formaldehyde is a satisfactory and useful one for imparting high wet strength to paper.

To' 194 parts of ethylendiamine of 93% purity at a temperature of C. there was slowly added 148.5 parts-of ethylene dichloride. The temperature during this addition was held be-' tween 100 and C. The reaction mixture was then heated to C. and held at this temperature until there was no more refluxing. The mixture was cooled to 90 C. and treated with 240 parts of aqueous 50% sodium hydroxide solution. The product at this point is on average triethylenetetramine.

It was heated to about 100 C. and treated with"118.8 parts of ethylene dichloride while the temperature was maintained between 100 and 110 C. The mixture was heated for an' hour at 110 to 112 C. and cooled to 90 C. The polyamine hydrochloride formed in this reaction was treated with 192 parts of aqueous 50% sodium hydroxide solution.

was slowly reacted with 90.1 parts of ethylene dichloride. The reaction mixture was heated until water was refluxed, cooled to 90 0., andtreated with 144 parts of aqueous 50% sodium hydroxide solution.

Again the reaction mixture was heated to 100- 110 C. and now treated with 29.7 parts of ethylene dichloride. The reaction mixture was heated until water was refluxed with the temperature of the mixture at 112 C. The mixture was cooled below 90 C. and treated with parts of aqueous" 50% sodium hydroxide solu- 1011.

A batch of 590 parts of the above mixture after treatment with sodium hydroxide solution was heated under reduced pressure with removal of about half of the water content. At this point 196 parts of urea were added and heating was continued with removal of the remaining portion of the water content. When the temperature reached 102 C. at 30 mm. pressure. heating was continued at atmospheric pressure.

Evolutionof ammonia began at 110C. The

batch was heated up to C. and held at this temperature for an hour. Water "was then added and the mixture was stirred for 15 minutes. With the temperature of the batch then reduced to 50 C. addition was made of 1580 parts of aqueous 37% formaldehyde solution.- The mixture was thoroughly stirred to yield 2179 parts of resin solution containing 34.2% of total solids. The sodium chloridecontent was 8.2% and the resin solids amounted to 26%. This solution had a viscosity of A on the Gardner- Holdt scale. It was highly effective for imparting wet strength to paper by addition to paper pulp in the beater.

Example ,7

parts had been used. Cooling was necessary durin the first part of this addition to control the temperature and toward the end of the additionheating was necessary to maintain the de-' sired temperature level. The reaction mixture was heated at 120 C. until the viscosity of a sample diluted with water in an amount of one third of the weight of the sample was in the range Q to R at 25 C. on the Gardner-Holdt scale.

The reaction mixture was thereupon cooled to about 100 C. and treated with 2120 parts of acqueous 50% sodium hydroxide solution. The mixture was cooled to 70 C. and 750 parts were added of ethylene dichloride. The mixture was heated to refluxing temperatures with the temperature thereof rising over a period of two hours to 112 C., at which temperature the reflux was water. The mixture was heated until the viscosity of a gram sample diluted with 7.5 grams of water was about C on the Gardner-Holdt scale. The reaction mixture was thereupon diluted with 1110 parts of water, cooled to 70 C. and treated with 1210 parts of aqueous 50% sodium hydroxide solution.

To this solution was added urea to an amount of 3490 parts. The resulting mixture was heated under reflux, the temperature being about 112 C. Under these conditions ammonia was evolved. Heating was continued until the viscosity of a sample, from which sodium chloride crystals were removed by centrifuging, was W on the Gardner-Holdt scale. Water was then distilled from the reaction mixture until 920 parts had been removed.

To this concentrate there were added 2140 parts of aqueous 37% formaldehyde solution. There was thus formed a resin solution amounting to 3200 parts, containing 38.4% of total solids and 31.2% of resin solids, and having a viscosity of A. This solution was highly effective for imparting wet strength to paper.

We claim:

1. A process of preparing resinous condensates which comprises reacting by heating together at 70 to 150 C. a dihaloalkane of not over three carbon atoms having a chain of two carbon atoms between the halogen atoms, said halogen being a member of the class consisting of chlorine and bromine, and a polyethylenepolyamine of a molecular weight of at least 146, the mole ratio of dihaloalkane to polyethylenepolyamine being at least 0.7:1 and not exceeding about 1.6:1 and being capable of yielding soluble condensation products, continuing reacting same until a 60% to 65% aqueous solution of the condensation products has a Gardner- Holdt viscosity of N to Z3 at 25 C., reacting said products by heating with urea between 100 and 200 C. until a 50% aqueous solution of the resulting reaction products has a Gardner-Holdt viscosity of about B to M at 25 C., the ratio of urea to --NH- groups of said nitrogenous condensation products being between 0.2:1 and 1.511, reacting said resulting reaction products in aqueous solution with formaldehyde to form soluble resinous condensates, there being used at least 0.6 mole of formaldehyde for each hydrogen presem on nitrogen in said nitrogeneous condensation products.

2. A process according to claim 1 wherein the dihaloalkane is a dichloroalkane.

3. A process according to claim 2 wherein the dichloroalkane is 1,2-dichloroethane.

4. The product obtained by the process of claim 1.

5. The product obtained by the process of claim 2.

6. The product obtained by the process of claim 3.

7. A process of preparing resinous condensates which comprises reacting by heating together at to 150 C. in the presence of water a dihaloalkane of not over three carbon atoms, the halogen thereof being a member of the class consisting of chlorine and bromine, and a polyethylenepolyamine having a molecular weight of at least 189, the mole ratio of dihaloalkane to polyethylenepolyamine being at least 07:1 and note ceeding 1.3:1 and yielding soluble polyamine hydrohalide condensation products, continuing reacting same until a 60% to 65% aqueous solution of the said condensation products has a Gardner-Holdt viscosity of U to Z1 at 25 0., adding a strong base in an amount to convert said polyamine hydrohalide condensation products to free polyamine condensation products, reacting them by heating them with urea between and C. until a 50% aqueous solution of the resulting reaction products has a Gardner-Holdt viscosity of about C to H at 25 C., the ratio of urea to NH groups of said condensation products being between 05:1 and 1.2:1, reacting in aqueous solution the said resulting reaction products with formaldehyde, there being used between 0.6 and 1.5 moles of formaldehyde for each hydrogen present on nitrogen in said reaction products, whereby soluble resinous condensates are formed.

8. A process according to claim 7 wherein the dihaloalkane is a dichloro compound.

9. A process according to claim 8 wherein the dichloroalkane is 1,2-dichloroethane.

10. The product obtained by the process of claim 7.

11. The product obtained by the process of claim 8.

12. The product obtained by the process of claim 9.

ROBERT S. YOST. ROBERT W. AUTEN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,554,475 Suen May 22, 1951 FOREIGN PATENTS Number Country Date 474,601 Great Britain Nov. 1, 1937 

1. A PROCESS OF PREPARING RESINOUS CONDENSATES WHICH COMPRISES REACTING BY HEATING TOGETHER AT 70* TO 150* C. A DIHALOALKANE OF NOT OVER THREE CARBON ATOMS HAVING A CHAIN OF TWO CARBON ATOMS BETWEEN THE HALOGEN ATOMS, SAID HALOGEN BEING A MEMBER OF THE CLASS CONSISTING OF CHLORINE AND BROMINE, AND A POLYETHYLENEPOLYAMINE OF A MOLECULAR WEIGHT OF AT LEAST 146, THE MOLE RATIO OF DIHALOALKANE TO POLYETHYLENEPOLYAMINE BEING AT LEAST 0.7:1 AND NOT EXCEEDING ABOUT 1.6:1 AND BEING CAPABLE OF YIELDING SOLUBLE CONDENSATION PRODUCTS, CONTINUING REACTING SAME UNTIL A 60% TO 65% AQUEOUS SOLUTION OF THE CONDENSATION PRODUCTS HAS A GARDNERHOLDT VISCOSITY OF N TO 23 AT 25* C., REACTING SAID PRODUCTS BY HEATING WITH UREA BETWEEN 100* AND 200* C. UNTIL A 50% AQUEOUS SOLUTION OF THE RESULTING REACTION PRODUCTS HAS A GARDNER-HOLDT VISCOSITY OF ABOUT B TO M AT 25* C., THE RATIO OF UREA TO -NH- GROUPS OF SAID NITROGENOUS CONDENSATION PRODUCTS BEING BETWEEN 0.2:1 AND 1.5:1, REACTING SAID RESULTING REACTION PRODUCTS IN AQUEOUS SOLUTION WITH FORMALDEHYDE TO FORM SOLUBLE RESINOUS CONDENSATES, THERE BEING USED AT LEAST 0.6 MOLE OF FORMALDEHYDE FOR EACH HYDROGEN PRESENT ON NITROGEN IN SAID NITROGENOUS CONDENSATION PRODUCTS. 